Patent GB-897187-A (GB)
Title: A process for the production of vanadyl trihalides and organic halides
IPC: C01G31/04
Filed: 1959-02-20
Abstract: <PICT:0897187/III/1> Vanadyl trihalides and halogenated organic compounds are prepared by reacting under anhydrous conditions solid vanadium oxides with an organic halide of formula <FORM:0897187/III/1> in which R1 is any group occupying the position normally occupied by hydrogen of the benzene ring, a C (halogen) group or a second aromatic ring condensed with the first ring and which may be substituted with a C (halogen) group, in vapour phase, at a temperature above the vaporization temperature of the organic halide reactant.  The reaction is preferably effected by passing the organic halide reactant through a bed of powdered vanadium pentoxide at 250 to 275 DEG  C. with sufficient velocity to fluidize it.  The vanadyl trichloride product may be separated from the organic products by fractionation.  As shown in Fig. 2, ammonium vanadate is fed to and fluidized in a column 1 by an upflowing stream of air at 500 to 600 DEG  C., thereby producing vanadium pentoxide, which is separated in separator 4 and passed to the bottom of a column 2, where it is fluidized by benzo trichloride fed from the bottom. Entrained unreacted vanadium pentoxide is removed and returned by separator 5, and the product vanadyl chloride together with benzoyl chloride are passed to a stripper rectifier 3, from the bottom of which the benzoyl chloride is removed and from the top of which the vanadyl chloride is recovered after passage through a condenser 6. The fluidization of the vanadium pentoxide in column 2 may be controlled by recycling benzo trichloride vapours through a pump 11 and heater 12.  Alternatively the reaction may be effected in a stirred static bed.  Suitable organic halide reactants are 1,3-bis(trichloromethyl benzene, 1,4-bis(trichloromethyl) benzene, benzotrichloride, 4,41-bis(trichloromethyl) biphenyl, which give rise respectively to isophthaloyl chloride, terephthaloyl chloride, benzoyl chloride and diphenyl-4-41-dicarbonylchloride.  The vanadyl trichloride may be reacted with aluminium alkyls to form an active olefine polymerization catalyst.  The invention is also applicable to the production of bromine and iodine derivatives.  Other organic compounds referred to are trichloromethyl naphthalenes, bis(trichloromethyl) naphthalenes, trichloromethyl anthracenes, bis(trichloromethyl) anthracenes, and trichloromethyl biphenyl. Other substitutents such as halogen, alkyl and/or aryl groups may be present on the benzene rings.ALSO:Organic halides containing a -CO(halogen) group are prepared by reacting under anhydrous conditions, vanadium oxide with the vapours of an organic halide of formula <FORM:0897187/IV (b)/1> in which R1 is any group occupying a position normally occupied by hydrogen, a -C(halogen)3 group or a second aromatic ring which may be condensed with the first ring and which may be substituted with a -C(halogen)3 group and other substituents such as halogen, alkyl and/or aryl groups. Particular reference is made to the production of benzoyl chloride, isophthaloyl chloride, terephthaloyl chloride, diphenyl-4,41-dicarbonyl chloride from benzotrichloride, 1,3-bis-(trichloromethyl) benzene, 1, 4 - bis (trichloromethyl) benzene and 4, 41-bis (trichloromethyl) biphenyl respectively.  Reference is also made to the employment as initial reactant of trichloromethyl naphthalenes, bis(trichloromethyl) naphthalenes, trichloromethyl biphenyl, trichloromethyl anthracenes and bis(trichloromethyl) anthracenes.  Bromine and iodine derivatives are also referred to.  Reaction may be effected at 250 DEG C.-275 DEG C. employing a fluidized bed of vanadium pentoxide. Vanadyl chloride produced may be separated by fractionation.